铂基氧还原催化剂：从单晶电极到拓展表面纳米材料

doi:10.11949/0438-1157.20231215

摘要/Abstract

摘要：

开发低成本、高性能的氧还原铂基催化剂仍然是目前推动质子交换膜燃料电池（PEMFC）商业化进程的重要方向。在拓展单晶电极表面的相关研究中，活性金属铂的原子排布、应力应变、周边配位环境等因素都被认为对氧还原的性能起到重要影响。然而，在规整表面的单晶电极上得到的经验并不能完全指导纳米催化剂的设计，这是因为纳米颗粒存在着尺寸效应带来的活性—利用率的矛盾关系。通过在纳米尺度上模拟单晶电极的性质，构造纳米薄膜材料及二维晶面可控的纳米材料，可以一定程度上实现拓展表面性质，打破矛盾关系。结合本课题组的研究工作，本文总结了拓展表面催化剂用于氧还原反应的理论和实验结果，探讨了纳米催化剂的发展和目前存在的问题，并对今后的研究方向进行了展望。

关键词: 氧还原, 燃料电池, 单晶电极, 纳米催化剂, 电化学, 氢

Abstract:

Developing low-cost oxygen reduction reaction catalysts with excellent activity remains a crucial issue in promoting the commercialization of proton exchange membrane fuel cell (PEMFC). The investigations of the single crystal electrode surface showed the factors such as the atomic arrangement, strain between lattices, and coordination environment of the Pt metal are responsible for the activity of oxygen reduction reaction. However, the knowledge gained from extended surfaces of single crystal electrodes cannot entirely guide the design of nanocatalysts due to the see-saw relationship between activity and utilization arising from size effects in nanoparticles. By simulating the properties of single crystal electrodes at the nanoscale, it is possible to expand surface properties and achieve the two-win results to some extent. This paper reviews the theoretical and experimental results regarding the use of extended surface catalysts for the oxygen reduction reaction, and the insights into the remaining challenges and research directions of nanocatalysts are also proposed.

Key words: oxygen reduction reaction, fuel cell, single crystal electrode, nanocatalysts, electrochemistry, hydrogen

中图分类号:

TQ 035

孙铭泽, 黄鹤来, 牛志强. 铂基氧还原催化剂：从单晶电极到拓展表面纳米材料[J]. 化工学报, DOI: 10.11949/0438-1157.20231215.

Mingze SUN, Helai HUANG, Zhiqiang NIU. Pt-based oxygen reduction reaction catalysts: from single crystal electrode to nanostructured extended surface[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231215.

图/表 6

图1 酸性条件下二电子和四电子ORR基本步骤(a)；OOH*和OH*中间体的线性相关关系(b)[27]；ORR过程的“火山型曲线”关系(c)[28]

Fig.1 2e- and 4e- mechanisms of ORR (a); Scaling relationship of OOH* and OH* intermediates (b); Volcano plot of ORR (c)

图2 台阶位点ORR提升的来源(a)[39]；Pt(111)腔体凹面结构会提升ORR活性(b)[40]；应变效应示意图(c)[44]；Pt与3d-过渡金属形成的合金薄膜材料ORR活性的实验(d)以及理论计算结果(e)[45]

Fig.2 Origin of the increase of ORR activity by step sites (a); Increase of ORR activities for defective Pt(111) cavity (b); Schematic illustration of strain effect (c); Specific activity (d) as well as theory calculation (e) of Pt and Pt3M electrodes

图3 八面体颗粒的尺寸与平台位点比例关系图(a)[71]；降低载量对催化剂性能的影响, 特别是在高电流密度下(b)[72]

Fig.3 Relationship between particle size and terrace site fraction(a); Influence of low Pt loading for ORR activity especially at high current density(b)

图4 NSTF催化剂的合成方法示意图(a)[84]；纳米气凝胶催化剂的合成示意图(b)[85]；螺旋式介孔网络Pt薄膜的合成示意图(c)[86]

Fig.2 Schematic illustration of the preperation and structure of NSTF catalyst (a); Schematic illustration of the synthesis of aerogel (b); Schematic illustration of the synthesis of meso-structured Pt (c)

图5 单个八面体纳米笼的HAADF-STEM图像(a)；八面体纳米笼、立方体纳米笼和TKK Pt/C在0.9 V时的SA和MA(b)[96]；PtPb/Pt六方纳米板的TEM图像(c)；稳定性测试后，PtPb/Pt六方纳米板催化剂的SA和MA的变化(d)[97]

Fig.5 HAADF-STEM image of an individual octahedral nanocage(a); Specific activities and mass activities at 0.9 V RHE of octahedral nanocages, cubic nanocages, and TKK Pt/C(b); TEM image of PtPb/Pt hexagonal nanoplates(c); Specific activities and mass activities of hexagonal nanoplates after stability test(d)

图6 PtCuNi 纳米管的合成示意图(a)；拓展面催化剂透射电镜表征（标尺：5 nm）(b)；EDS mapping 呈现出Cu@PtNi的核壳结构（标尺：5 nm）(c)；PtCuNiAu纳米管、PtCuNi 纳米管、PtCuNi NPs 和商用Pt/C在0.9 V时的SA和MA(d)；PtCuNi纳米管和商用Pt/C的H2-空气燃料电池极化曲线和功率密度图(e)[102]

Fig.6 Schematic illustration of the synthesis of extended PtCuNi catalyst(a); Representative HAADF-STEM image of Cu@PtNi core–shell nanowire. Scale bar, 5nm(b); EDS elemental mapping of Cu@PtNi core–shell nanowire. Scale bar, 5nm(c); Specific activities and mass activities at 0.9 V RHE of extended PtCuNiAu, extended PtCuNi, PtCuNi NPs and commercial Pt/C(d); H2-air fuel cell polarization and power density plots of commercial Pt/C and extended PtCuNi(e)

参考文献 102

1	Hassan Q, Sameen A Z, Salman H M, et al. Hydrogen energy future: Advancements in storage technologies and implications for sustainability[J]. Journal of Energy Storage, 2023, 72: 108404.
2	Pathak P K, Yadav A K, Padmanaban S. Transition toward emission-free energy systems by 2050: potential role of hydrogen[J]. International Journal of Hydrogen Energy, 2023, 48(26): 9921-9927.
3	Abe J O, Popoola A P I, Ajenifuja E, et al. Hydrogen energy, economy and storage: Review and recommendation[J]. International Journal of Hydrogen Energy, 2019, 44(29): 15072-15086.
4	Yusaf T, Faisal Mahamude A S, Kadirgama K, et al. Sustainable hydrogen energy in aviation–A narrative review[J]. International Journal of Hydrogen Energy, 2024, 52: 1026-1045.
5	Dyantyi N, Parsons A, Bujlo P, et al. Behavioural study of PEMFC during start-up/shutdown cycling for aeronautic applications[J]. Materials for Renewable and Sustainable Energy, 2019, 8(1): 4.
6	Wang X Y, Zhu J Z, Han M F. Industrial development status and prospects of the marine fuel cell: a review[J]. Journal of Marine Science and Engineering, 2023, 11(2): 238.
7	Zhan Z P. Current status and future development of fuel cell ships in China[J]. Journal of Physics: Conference Series, 2022, 2160(1): 012061.
8	Debe M K. Electrocatalyst approaches and challenges for automotive fuel cells[J]. Nature, 2012, 486: 43-51.
9	Zhu X Y, Gui P P, Zhang X X, et al. Multi-objective optimization of a hybrid energy system integrated with solar-wind-PEMFC and energy storage[J]. Journal of Energy Storage, 2023, 72, 108562.
10	Shao M H, Chang Q W, Dodelet J P, et al. Recent advances in electrocatalysts for oxygen reduction reaction[J]. Chemical Reviews, 2016, 116(6): 3594-3657.
11	Hu X Y, Yang B Z, Ke S R, et al. Review and perspectives of carbon-supported platinum-based catalysts for proton exchange membrane fuel cells[J]. Energy & Fuels, 2023, 37(16): 11532-11566.
12	Zhang X, Xie Y, Wang L. Progress and prospect of Pt-based catalysts for electrocatalytic hydrogen oxidation reactions[J]. Nano Research, 2024, 17(3): 960-981.
13	James B.; Huya-Kouadio J, Houchins C, et al. Heavy-Duty Fuel Cell System Cost – 2022; DOE Hydrogen and Fuel Cells Program, 2023. .
14	Duan Z Y, Wang G F. Comparison of reaction energetics for oxygen reduction reactions on Pt(100), Pt(111), Pt/Ni(100), and Pt/Ni(111) surfaces: a first-principles study[J]. The Journal of Physical Chemistry C, 2013, 117(12): 6284-6292.
15	Dong J C, Zhang X G, Briega-Martos V, et al. In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces[J]. Nature Energy, 2019, 4: 60-67.
16	Wang T, Zhang Y R, Huang B T, et al. Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds[J]. Nature Catalysis, 2021, 4: 753-762.
17	Chen C H, Meadows K E, Cuharuc A, et al. High resolution mapping of oxygen reduction reaction kinetics at polycrystalline platinum electrodes[J]. Physical Chemistry Chemical Physics, 2014, 16(34): 18545-18552.
18	Temmel S E, Fabbri E, Pergolesi D, et al. Investigating the role of strain toward the oxygen reduction activity on model thin film Pt catalysts[J]. ACS Catalysis, 2016, 6(11): 7566-7576.
19	Ahluwalia R K, Wang X, Lajunen A, et al. Kinetics of oxygen reduction reaction on nanostructured thin-film platinum alloy catalyst[J]. Journal of Power Sources, 2012, 215: 77-88.
20	Zhang J M, Yang H B, Zhou D J, et al. Adsorption energy in oxygen electrocatalysis[J]. Chemical Reviews, 2022, 122(23): 17028-17072.
21	Zhao J Y, Lian J X, Zhao Z, et al. A review of In-situ techniques for probing active sites and mechanisms of electrocatalytic oxygen reduction reactions[J]. Nano-Micro Letters, 2022, 15(1): 19.
22	Tang C, Chen L, Li H J, et al. Tailoring acidic oxygen reduction selectivity on single-atom catalysts via modification of first and second coordination spheres[J]. Journal of the American Chemical Society, 2021, 143(20): 7819-7827.
23	Huang H L, Sun M Z, Li M, et al. Recent advances in single-atom catalysts for electrocatalytic synthesis of hydrogen peroxide[J]. Green Energy and Resources, 2023, 1(3): 100031.
24	Zhang Y X, Zhang S B, Huang H L, et al. General synthesis of a diatomic catalyst library via a macrocyclic precursor-mediated approach[J]. Journal of the American Chemical Society, 2023, 145(8): 4819-4827.
25	Sun M Z, Gong S Y, Zhang Y-X, et al. A perspective on the PGM-free metal–nitrogen–carbon catalysts for PEMFC[J]. Journal of Energy Chemistry, 2022, 67: 250-254.
26	Zhang S B, Wu Y F, Zhang Y-X, et al. Dual-atom catalysts: controllable synthesis and electrocatalytic applications[J]. Science China Chemistry, 2021, 64(11): 1908-1922.
27	Viswanathan V, Hansen H A, Rossmeisl J, et al. Universality in oxygen reduction electrocatalysis on metal surfaces[J]. ACS Catalysis, 2012, 2(8): 1654-1660.
28	Xie C L, Niu Z Q, Kim D, et al. Surface and interface control in nanoparticle catalysis[J]. Chemical Reviews, 2020, 120(2): 1184-1249.
29	Gao G P, Waclawik E R, Du A J. Computational screening of two-dimensional coordination polymers as efficient catalysts for oxygen evolution and reduction reaction[J]. Journal of Catalysis, 2017, 352: 579-585.
30	Calle-Vallejo F, Krabbe A, García-Lastra J M. How covalence breaks adsorption-energy scaling relations and solvation restores them[J]. Chemical Science, 2017, 8(1): 124-130.
31	Tritsaris G A, Greeley J, Rossmeisl J, et al. Atomic-scale modeling of particle size effects for the oxygen reduction reaction on Pt[J]. Catalysis Letters, 2011, 141(7): 909-913.
32	Hammer B, Nørskov J K. Why gold is the noblest of all the metals[J]. Nature, 1995, 376: 238-240.
33	Hammer B, Nørskov J K. Theoretical surface science and catalysis—calculations and concepts[M]//Advances in Catalysis. Amsterdam: Elsevier, 2000: 71-129.
34	Nilsson A, Pettersson L G M, Hammer B, et al. The electronic structure effect in heterogeneous catalysis[J]. Catalysis Letters, 2005, 100(3): 111-114.
35	Zhu X J, Guo Q S, Sun Y F, et al. Optimising surface d charge of AuPd nanoalloy catalysts for enhanced catalytic activity[J]. Nature Communications, 2019, 10: 1428.
36	Kitchin J R, Nørskov J K, Barteau M A, et al. Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals[J]. The Journal of Chemical Physics, 2004, 120(21): 10240-10246.
37	Marković N M, Adžić R R, Cahan B D, et al. Structural effects in electrocatalysis: oxygen reduction on platinum low index single-crystal surfaces in perchloric acid solutions[J]. Journal of Electroanalytical Chemistry, 1994, 377(1/2): 249-259.
38	Marković N M, Gasteiger H A, Ross P N. Oxygen reduction on platinum low-index single-crystal surfaces in sulfuric acid solution: rotating ring-Pt(hkl) disk studies[J]. The Journal of Physical Chemistry, 1995, 99(11): 3411-3415.
39	Hoshi N, Nakamura M, Hitotsuyanagi A. Active sites for the oxygen reduction reaction on the high index planes of Pt[J]. Electrochimica Acta, 2013, 112: 899-904.
40	Calle-Vallejo F, Tymoczko J, Colic V, et al. Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors[J]. Science, 2015, 350(6257): 185-189.
41	Calle-Vallejo F, Martínez J I, García-Lastra J M, et al. Fast prediction of adsorption properties for platinum nanocatalysts with generalized coordination numbers[J]. Angewandte Chemie International Edition, 2014, 53(32): 8316-8319.
42	Calle-Vallejo F, Pohl M D, Reinisch D, et al. Why conclusions from platinum model surfaces do not necessarily lead to enhanced nanoparticle catalysts for the oxygen reduction reaction[J]. Chemical Science, 2017, 8(3): 2283-2289.
43	Calle-Vallejo F, Bandarenka A S. Enabling generalized coordination numbers to describe strain effects[J]. ChemSusChem, 2018, 11(11): 1824-1828.
44	Luo M C, Guo S J. Strain-controlled electrocatalysis on multimetallic nanomaterials[J]. Nature Reviews Materials, 2017, 2(11): 17059.
45	Stamenkovic V, Mun B S, Mayrhofer K J J, et al. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure[J]. Angewandte Chemie International Edition, 2006, 118(18): 2963-2967.
46	Strasser P, Koh S, Anniyev T, et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts[J]. Nature Chemistry, 2010, 2: 454-460.
47	Wang Z C, Chen S H, Wu W, et al. Tailored lattice compressive strain of Pt-skins by the L1₂-Pt₃M intermetallic core for highly efficient oxygen reduction[J]. Advanced Materials, 2023, 35(36): e2301310.
48	Yang W H, Zou L L, Huang Q H, et al. Lattice contracted ordered intermetallic core-shell PtCo@Pt nanoparticles: synthesis, structure and origin for enhanced oxygen reduction reaction[J]. Journal of the Electrochemical Society, 2017, 164(6): H331-H337.
49	Stephens I E L, Bondarenko A S, Perez-Alonso F J, et al. Tuning the activity of Pt(111) for oxygen electroreduction by subsurface alloying[J]. Journal of the American Chemical Society, 2011, 133(14): 5485-5491.
50	Hernandez-Fernandez P, Masini F, McCarthy D N, et al. Mass-selected nanoparticles of Pt_xY as model catalysts for oxygen electroreduction[J]. Nature Chemistry, 2014, 6: 732-738.
51	Escudero-Escribano M, Malacrida P, Hansen M H, et al. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction[J]. Science, 2016, 352(6281): 73-76.
52	Li J, Li L, Wang M J, et al. Alloys with Pt-skin or Pt-rich surface for electrocatalysis[J]. Current Opinion in Chemical Engineering, 2018, 20: 60-67.
53	van der Vliet D F, Wang C, Li D G, et al. Unique electrochemical adsorption properties of Pt-skin surfaces[J]. Angewandte Chemie International Edition, 2012, 51(13): 3139-3142.
54	Wang C, Chi M F, Li D G, et al. Design and synthesis of bimetallic electrocatalyst with multilayered Pt-skin surfaces[J]. Journal of the American Chemical Society, 2011, 133(36): 14396-14403.
55	Stamenkovic V R, Mun B S, Mayrhofer K J J, et al. Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces[J]. Journal of the American Chemical Society, 2006, 128(27): 8813-8819.
56	Wang G W, Huang B, Xiao L, et al. Pt skin on AuCu intermetallic substrate: a strategy to maximize Pt utilization for fuel cells[J]. Journal of the American Chemical Society, 2014, 136(27): 9643-9649.
57	Stamenkovic V R, Fowler B, Mun B S, et al. Improved oxygen reduction activity on Pt₃Ni(111) via increased surface site availability[J]. Science, 2007, 315(5811): 493-497.
58	Huang X Q, Zhao Z P, Cao L, et al. High-performance transition metal–doped Pt₃Ni octahedra for oxygen reduction reaction[J]. Science, 2015, 348(6240): 1230-1234.
59	Wang S J, Sheng T, Yuan Q. Low-Pt octahedral PtCuCo nanoalloys: "one stone, four birds" for oxygen reduction and methanol oxidation reactions[J]. Inorganic Chemistry, 2023, 62(29): 11581-11588.
60	Kong F P, Ren Z H, Norouzi Banis M, et al. Active and stable Pt–Ni alloy octahedra catalyst for oxygen reduction via near-surface atomical engineering[J]. ACS Catalysis, 2020, 10(7): 4205-4214.
61	Luo Y Y, Lou W H, Feng H Y, et al. Ultra-small nanoparticles of Pd-Pt-Ni alloy octahedra with high lattice strain for efficient oxygen reduction reaction[J]. Catalysts, 2023, 13(1): 97.
62	常丰瑞, 黄俭标, 马建新, 等. PEMFC用Pt纳米线阴极催化剂的制备及在电堆中的应用[J]. 化工学报, 2014, 65(10): 3891-3898.
	Chang F R, Huang J B, Ma J X, et al. Preparation of Pt nanowires as cathode catalyst for PEMFC and its application in stack[J]. CIESC Journal, 2014, 65(10): 3891-3898.
63	Inaba M, Zana A, Quinson J, et al. The oxygen reduction reaction on Pt: why particle size and interparticle distance matter[J]. ACS Catalysis, 2021, 11(12): 7144-7153.
64	Gan J, Luo W, Chen W Y, et al. Mechanistic understanding of size-dependent oxygen reduction activity and selectivity over Pt/CNT nanocatalysts[J]. European Journal of Inorganic Chemistry, 2019, 2019(27): 3210-3217.
65	Van Helden P, Ciobîca I M, Coetzer R L J. The size-dependent site composition of FCC cobalt nanocrystals[J]. Catalysis Today, 2016, 261: 48-59.
66	Kodama K, Nagai T, Kuwaki A, et al. Challenges in applying highly active Pt-based nanostructured catalysts for oxygen reduction reactions to fuel cell vehicles[J]. Nature Nanotechnology, 2021, 16: 140-147.
67	Yuan Y, Yan N, Dyson P J. Advances in the rational design of rhodium nanoparticle catalysts: control via manipulation of the nanoparticle core and stabilizer[J]. ACS Catalysis, 2012, 2(6): 1057-1069.
68	Fan L H, Deng H, Zhang Y G, et al. Towards ultralow platinum loading proton exchange membrane fuel cells[J]. Energy & Environmental Science, 2023, 16(4): 1466-1479.
69	Patil V, Reshmi P V, Prajna S, et al. Degradation mechanisms in PEM fuel cells: A brief review[J]. Materials Today: Proceedings, 2023, doi.org/10.1016/j.matpr.2023.03.603.
70	Miao Z P, Li S Z, Priest C, et al. Effective approaches for designing stable M-N_x/C oxygen-reduction catalysts for proton-exchange-membrane fuel cells[J]. Advanced Materials, 2022, 34(52): e2200595.
71	Sun M Z, Gong S Y, Li Z W, et al. Terrace-rich ultrathin PtCu surface on earth-abundant metal for oxygen reduction reaction[J]. ACS Nano, 2023, 17(19): 19421-19430.
72	Greszler T A, Caulk D, Sinha P. The impact of platinum loading on oxygen transport resistance[J]. Journal of the Electrochemical Society, 2012, 159(12): F831-F840.
73	Zhao Z P, Chen C L, Liu Z Y, et al. Pt-based nanocrystal for electrocatalytic oxygen reduction[J]. Advanced Materials, 2019, 31(31): e1808115.
74	Kongkanand A, Mathias M F. The priority and challenge of high-power performance of low-platinum proton-exchange membrane fuel cells[J]. The Journal of Physical Chemistry Letters, 2016, 7(7): 1127-1137.
75	Pan L J, Ott S, Dionigi F, et al. Current challenges related to the deployment of shape-controlled Pt alloy oxygen reduction reaction nanocatalysts into low Pt-loaded cathode layers of proton exchange membrane fuel cells[J]. Current Opinion in Electrochemistry, 2019, 18: 61-71.
76	Cao F, Ding R, Rui Z Y, et al. Advances in low Pt loading membrane electrode assembly for proton exchange membrane fuel cells[J]. Molecules, 2023, 28(2): 773.
77	Zaman S, Douka A I, Noureen L, et al. Oxygen reduction performance measurements: discrepancies against benchmarks[J]. Battery Energy, 2023, 2(3): 20220060.
78	Zaman S, Tian X L, Xia B Y. Bridging oxygen reduction performance gaps in half and full cells: challenges and perspectives[J]. Materials Chemistry Frontiers, 2023, 7(20): 4605-4612.
79	Li J R, Liu M X, Liu X, et al. The recent progress of oxygen reduction electrocatalysts used at fuel cell level[J]. Small Methods, 2024, 8(3): e2301249.
80	Luo M C, Guo S J. Multimetallic electrocatalyst stabilized by atomic ordering[J]. Joule, 2019, 3(1): 9-10.
81	Liu J Y, Liu S Y, Yan F Z, et al. Ultrathin nanotube structure for mass-efficient and durable oxygen reduction reaction catalysts in PEM fuel cells[J]. Journal of the American Chemical Society, 2022, 144(41): 19106-19114.
82	Li J L, Liu H Y, Zhang W Q, et al. In-situ preparation of low Pt loading multi rhombic-pyramidal Pt-Pd catalyst layer for high-performance proton exchange membrane fuel cells[J]. Journal of Power Sources, 2023, 556: 232445.
83	van der Vliet D, Wang C, Debe M, et al. Platinum-alloy nanostructured thin film catalysts for the oxygen reduction reaction[J]. Electrochimica Acta, 2011, 56(24): 8695-8699.
84	van der Vliet D F, Wang C, Tripkovic D, et al. Mesostructured thin films as electrocatalysts with tunable composition and surface morphology[J]. Nature Materials, 2012, 11: 1051-1058.
85	Liu W, Herrmann A K, Bigall N C, et al. Noble metal aerogels-synthesis, characterization, and application as electrocatalysts[J]. Accounts of Chemical Research, 2015, 48(2): 154-162.
86	Liu W, Rodriguez P, Borchardt L, et al. Bimetallic aerogels: high-performance electrocatalysts for the oxygen reduction reaction[J]. Angewandte Chemie International Edition, 2013, 52(37): 9849-9852.
87	Liu W, Herrmann A K, Geiger D, et al. High-performance electrocatalysis on palladium aerogels[J]. Angewandte Chemie International Edition, 2012, 51(23): 5743-5747.
88	Hwang C K, Kim J M, Hwang S, et al. Porous strained Pt nanostructured thin-film electrocatalysts via dealloying for PEM fuel cells[J]. Advanced Materials Interfaces, 2020, 7(2): 1901326.
89	Kibsgaard J, Gorlin Y, Chen Z B, et al. Meso-structured platinum thin films: active and stable electrocatalysts for the oxygen reduction reaction[J]. Journal of the American Chemical Society, 2012, 134(18): 7758-7765.
90	Beermann V, Gocyla M, Willinger E, et al. Rh-doped Pt-Ni octahedral nanoparticles: understanding the correlation between elemental distribution, oxygen reduction reaction, and shape stability[J]. Nano Letters, 2016, 16(3): 1719-1725.
91	Meier J C, Galeano C, Katsounaros I, et al. Design criteria for stable Pt/C fuel cell catalysts[J]. Beilstein Journal of Nanotechnology, 2014, 5: 44-67.
92	Mayrhofer K J J, Blizanac B B, Arenz M, et al. The impact of geometric and surface electronic properties of Pt-catalysts on the particle size effect in electrocatalysis[J]. The Journal of Physical Chemistry B, 2005, 109(30): 14433-14440.
93	Han B H, Carlton C E, Kongkanand A, et al. Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells[J]. Energy & Environmental Science, 2015, 8(1): 258-266.
	Marković N M, Ross P N. Surface science studies of model fuel cell electrocatalysts[J]. Surface Science Reports, 2002, 45(4): 117-229.
95	Todoroki N, Kato T, Hayashi T, et al. Pt–Ni nanoparticle-stacking thin film: highly active electrocatalysts for oxygen reduction reaction[J]. ACS Catalysis, 2015, 5(4): 2209-2212.
96	Zhang L, Roling L T, Wang X, et al. Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets[J]. Science, 2015, 349(6246): 412-416.
97	Bu L Z, Zhang N, Guo S J, et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis[J]. Science, 2016, 354(6318): 1410-1414.
98	Xie M H, Lyu Z H, Chen R H, et al. Pt-Co@Pt octahedral nanocrystals: enhancing their activity and durability toward oxygen reduction with an intermetallic core and an ultrathin shell[J]. Journal of the American Chemical Society, 2021, 143(22): 8509-8518.
99	Li Z, Ji S F, Liu Y W, et al. Well-defined materials for heterogeneous catalysis: from nanoparticles to isolated single-atom sites[J]. Chemical Reviews, 2020, 120(2): 623-682.
100	Gong S Y, Zhang Y X, Niu Z Q. Recent advances in earth-abundant core/noble-metal shell nanoparticles for electrocatalysis[J]. ACS Catalysis, 2020, 10(19): 10886-10904.
101	Ding H, Wang P, Su C J, et al. Epitaxial growth of ultrathin highly crystalline Pt-Ni nanostructure on a metal carbide template for efficient oxygen reduction reaction[J]. Advanced Materials, 2022, 34(12): e2109188.
102	Gong S Y, Sun M Z, Lee Y Y, et al. Bulk-like Pt(100)-oriented ultrathin surface: combining the merits of single crystals and nanoparticles to boost oxygen reduction reaction[J]. Angewandte Chemie International Edition, 2023, 62(4): 2214516.

[1]	王雪杰, 崔国庆, 王文涵, 杨扬, 王淙恺, 姜桂元, 徐春明. 电内加热Pt/NPC催化剂高效催化甲基环己烷脱氢反应研究[J]. 化工学报, 2024, 75(1): 292-301.
[2]	闫可欣, 姜洪涛, 高维群, 郭晓晖, 孙伟振, 赵玲. 电子级多晶硅原料中痕量硼磷杂质的脱除研究进展[J]. 化工学报, 2024, 75(1): 83-94.
[3]	闻文, 王慧艳, 周静红, 曹约强, 周兴贵. 石墨负极颗粒对锂离子电池容量衰减及SEI膜生长影响的模拟研究[J]. 化工学报, 2024, 75(1): 366-376.
[4]	齐元帅, 彭文朝, 李阳, 张凤宝, 范晓彬. 电化学脱盐机理及相关研究进展[J]. 化工学报, 2024, 75(1): 171-189.
[5]	朱娇, 栾丽萍, 从深震, 刘新磊. 氢气分离有机膜[J]. 化工学报, 2024, 75(1): 138-158.
[6]	杨欣, 王文, 徐凯, 马凡华. 高压氢气加注过程中温度特征仿真分析[J]. 化工学报, 2023, 74(S1): 280-286.
[7]	黄琮琪, 吴一梅, 陈建业, 邵双全. 碱性电解水制氢装置热管理系统仿真研究[J]. 化工学报, 2023, 74(S1): 320-328.
[8]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[9]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[10]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[11]	曹跃, 余冲, 李智, 杨明磊. 工业数据驱动的加氢裂化装置多工况切换过渡状态检测[J]. 化工学报, 2023, 74(9): 3841-3854.
[12]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[13]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[14]	李科, 文键, 忻碧平. 耦合蒸气冷却屏的真空多层绝热结构对液氢储罐自增压过程的影响机制研究[J]. 化工学报, 2023, 74(9): 3786-3796.
[15]	陆俊凤, 孙怀宇, 王艳磊, 何宏艳. 离子液体界面极化及其调控氢键性质的分子机理[J]. 化工学报, 2023, 74(9): 3665-3680.